Synthetic lubricants



March 14, 1950 F, M. SEGER ET AL. 2,500,166

` SYNTHETIC LUBRICANTS n r( 6 6 2 Mew N 0, w 0 NS( R 0 h Z E.a m. 5 WM5. 9u c/ I 5 H r 1 F .ar m m@ 0 w M 3 /v 6 W ma mm 1 u, n 0 5 Y u e u um m s E Ab ZU 2W m 1w 4 l@ am 5 F f X H me a E f f f mf, s f m 0 70S M Mm .0N F. w m N U w GH 4 bf E X R E 4 f R NC F 2 wf a Z @K ma 0 0 0 0 0 M 0 0 0 0 0 Fl w March 14, 1950 F'lled July 15 1949 March 14, 1950 F. M. sEGl-:R ETAL SYNTHETIC LUBRICANTS sul 6 l, 0 0 5,- 2

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. und W @haw Patented Mar. i4, 1950 SYNTHETIC LUBRICANTS Francis M. Seger, Pitman, and Alexander N.

Sachanen, Woodbury, N. J., asslgnors to Socony-Vacuum Oil Company, Incorporated, a

corporation of New York Application July 15, 1949, Serial No. 104,932 In Canada April 3, 1948 claims. l

This invention relates to new synthetic lubricants characterized by an especially desirable combination of low pour point, high viscosity index and good stability, and to a method for their manufacture. More particularly, this invention relates to the efficient manufacture of synthetic lubricants having this highly desirable combination of characteristics from mixtures of normally liquid straight-chain 1olens containing from six to twelve carbon atoms, by thermal, but non-catalytic treatment of the olens.

This application is a continuation-in-part of our application, Serial No. 761,716, filed July 17, 1947, now abandoned.

Polymerization and condensation reactions in general have long been accomplished by the use of either heat or catalysts or both. Oleilns have been catalytically polymerized to form oils, particularly with Friedel-Crafts type catalysts such as aluminum chloride. It has been found that cyclic and highly branched oleiins are converted in the presence of AlCla to oils of poor viscosity index (V. 1.), while oils obtained from normal or straight chain olens with the same catalyst have much better V. I. This is described in detail by Sullivan, Voorhees, Neely and Shankland in Industrial and Engineering Chemistry, 23, 604-611 (June 1931), as Well as by Koch and Hilberath in Brennstoffe Chemie, 23, 67 (1942). Olelins have also been polymerized to higher oleilns when heated in the presence of small amounts of oxygen, at temperatures of 400700 C. (752-1292 F.) for several seconds, as described by Lenher in United States Letters Patent N0. 2,000,964. In the latter process, for example, an olen such as ethylene is polymerized to propylene and, to a lesser degree, to butylene and amylenes.

As indicated above, oleflns have also been polymerized by heat alone. By way of illustration, Batchelder and Kuentzel have converted normally gaseous olefins, such as ethylene, into high viscosity index lubricants in the absence of active catalysts, at temperatures of 500 F. to 750 F.; this is described in United States Letters Patent 2,111,831. Engler and Routala-Berichte, 42, 4620 (1909)--heated methyl butene-2 at 320- 325 C. (60S-617 F.) for 32 days and obtained a small quantity of an oily residue. Hexene-2 was similarly treated, with the formation of a small amount of lubricating oil. Nemtzov et a1.-J. Genl. Chem. (Russ) 8, 1314-1324 1938)--therrna1ly polymerized a mixture of straight chain octenes, with the ratio of alphaand beta- (or 1- and 2) isomers approximately 40:60. The products obtained from such an oleiin charge were principally octene dimers, containing only a very small quantity of higher polymers. Tilicheyev and Feigin--Proc- Conference on Cracking (Russ), 269-280 (1931)--thermal1y 2 polymerized caprylene and hexadecenc, at a temperature of 425 C. (797 F.)

Polymerization and cracking of olens have also been described by Hugel and Cohn (Chimie & Industrie, Special No. 201-202 (March 1930)). An alpha octene, having a boiling point of 122- 123 C., was thermally treated at 400 C. (752 F.) under pressure; hexadecene was similarly treated at 300 C. (572 F.) for twenty-four hours.

The polymers obtained by such thermal treatments were primarily dimers and trimers, and the products obtained from hexadecene were solids or semi-solids resembling paraiiin wax. Thermal polymerization of hexadecene is further described by Hugel and Artichevitch, Annales Com-- bustibles Liquides, 3, 985-1027 (1928) and by Hugel and Kohn, Annales Combustibles Liquides, 7, 15-54 (1932).

Prior to the present invention described in our aforesaid application, however. it was not known that straight chain 1-olefns such as normal decene-l could be polymerized or condensed by heat alone to form synthetic oils in commercially feasible yields, such oils having an exceptional combination of properties. Briey, the invention is based upon the discovery that straight-chain 1- olens containing between six and about twelve carbon atoms per molecule are converted into synthetic oils having an exceptionally desirable combination of characteristics when thermally treated, in the absence of catalysts and under controlled reaction conditions.

The oils of this invention diier from oils produced catalytically, or by a combination of catalytic and thermal treatments, in that the characteristics of the resultant oils are quite different and far more desirable. Prior to this invention it was not kown that oils could be produced in the manner herein described, at all, and, oi course, it was therefore not known that oils thus produced would have an unusually desirable combination of characteristics. Quite unexpectedly the oils of the present invention possess a combination of very low pour point, very high viscosity index and very good stability. Bromine addition tests indicate the existence of a considerable degree of unsaturation, but this does not appear to aiect the stability.

Reactants The reactants for the production of synthetic oils in accordance with this invention are normally liquid, straight-chain 1-olens ranging from hexene-l to dodecene-l, inclusive. It must be clearly understood that by straight-chain 1- olens we mean mono-olefins containing the double bond in the alpha position and having a normal structure. In accordance with our invention, the most desirable synthetic oils are produced from straight-chain l-oleiins containing not less than eight nor more than eleven carbon atoms per molecule.

The state of purity of the straight-chain 1-oleiin charge does not appear to be especially critical. Although it is desirable to have a starting material which contains as large a percentage of the above described 1-oleiins as possible, it is permissible to have present lesser amounts of other olens and of other hydrocarbon materials. In general, the olenic charge stock preferably should contain less than about by weight of unsaturated hydrocarbons other than straightchain l-oleflns having not less than six nor more than about twelve carbon atoms per molecule. However, since paralns are not involved in polymerization, we have found that charge stocks containing as much as 50% by weight of parailinic hydrocarbons with the balance straight-chain l-olens having between six and about twelve carbon atoms per molecule are entirely satisfactory for our purpose. In many instances, in commercial operation, it will be found desirable to use technical grades of such olefins as'octene-l or decene-l. Mixed oleilnic materials derived from the thermal cracking of wax or from the Fischer- Tropsch process constitute satisfactory charging stocks. In this connection, it must be noted that it is suspected that substantially straight-chain 1olefns having beween six and about twelve carbon atoms per molecule, i. e., l-olefins in which the length of side chain or chains is short relative to the length of the main chain, are also suitable, although less preferred charge stocks for the purpose of the present invention. However, in view of the fact that such oleiins are unavailable, no test data can be adduced to confirm this suspicion.

It will be understood, therefore, that the reactant or charge material used herein is of 'hydrocarbon character and predominantly comprised of at least one of the normal, alpha mono-olens described above.

Synthetic lubricants made from substantially pure normal, alpha mono-oleiins under the conditions described below, are oils of medium viscosity, pale color and good stability. When an oleflnic charge stock highly contaminated with aromatic hydrocarbons or with oxygen-containing materials, is used, a product of inferior character is generally obtained. While this condition has not been thoroughly correlated with charge distribution, it has been observed that olenic charge stocks so contaminated give rise to unstable products which are not suited for lubricating oil use. This is evidenced by a very dark color, excessive carbon residue (Conradson or Ramsbottom), and a tendency to deposit dark insoluble materials on storage.

Tests indicate that when relatively pure, single oleiins are used theyshould preferably contain not less than seven nor more than eleven carbon atoms per molecule, although mixtures of olens containing an average of as few as six or as many as twelve carbon atoms per molecule are satisfactory.

REACTION CONDITIONS The most critical reaction condition is temperature, and this condition is closely interrelated with reaction time and pressure. The range of temperatures that produces satisfactory, commercially feasible yields of high quality synthetic oils varies from about 600 F. to about 700 F. At temperatures between 500 F. and 600 F. the conversion takes place at a slower rate and is usually less complete. At temperatures greater than 700 F., side and secondary reactions begin to occur and increase in importance to such an extent that at temperatures above about 750 F. the process again becomes impracticable.

These side and secondary reactions are chiefly the following:

1. The volatile non-oily components of the reaction mixture become progressively more saturated, as indicated by a decrease in bromine addition number and, therefore, less suitable for recycling for further conversion;

2. Cracking begins, as evidenced by greater gas pressure and decrease in oil yields; and

3. Cyclization begins, as evidenced by some decline in viscosity index with accompanying increase in gravity and refractive index.

The time of reaction varies inversely with temperature and, as indicated above, is closely interrelated with temperature. Good products and good yields have been produced with times as short as one hour or less at temperatures of the order of 750 F., and as long as thirty hours at temperatures of about 600 F. Advantageously, the time is in the neighborhood of five to twenty hours at about 600 F., and one to five hours at 700 F. A range of time of from three to twenty hours at temperatures ranging from 650 F. to about 600 F. is considered most advantageous for straight-chain l-oleflns having eight to eleven carbon atoms per molecule.

Test data also indicate that reasonable yields of products of comparatively high viscosity index may be obtained at temperatures of 750 F. to 800 F. and times of several minutes. These conditions are less advantageous, however, because the products frequently have higher pour points, and the material that is not converted into oil is partially degraded into light fractions of a relatively low degree of unsaturation which are therefore much less desirable as recycle stock. The viscosity index decreases sharply with prolonged exposure to these higher temperatures.

Pressure to be used is not especially critical. It will usually be around 200 to 1000 pounds per square inch or higher depending upon the vapor pressure of the olefin reactant. Increased pressure is desirable, and, as expected, increases the oil yields, particularly at the comparatively higher temperatures (as '700-'750 F.) and with the lower molecular weight oleiins (e. g., Cs-Ca). The use of pressures of at least about pounds per square inch is within the scope of this invention, with pressures upwards of 500 pounds per square inch being preferred.

It is within the scope of this invention to perform the reaction or conversion either by a batch process or a continuous process, and to recycle unconverted olefin reactant or partially converted olefin reactant for further conversion.

Further details and advantages of this invention are illustrated by the following examples which have been set forth in tabular form below. The reactions or conversions summarized in the table were conducted in shaker-type pressure bombs (American Instrument Co.) and the autogeneous pressure due to the heating of the olefin reactant was used. The olefin charges were charged to the bombs, the bomb heads secured and the bombs flushed with nitrogen (unless indicated otherwise) to displace air present therein. The bombs were then heated (while rocked) to the desired temperature for the desired length of time. Thereafter, the bombs were either cooled and discharged, or discharged immediately through a condensing system while the bombs were still at the reaction temperature.

It should be noted that the reaction times, recited as time. hours in the tables, represent the time intervals during which the bombs were maintained at the desired temperature, and do not include the time intervals necessary to heat 5 will be noted that the designation "N. N. refers to the neutralization number, which is a measure of the acidity of the oil. The Saybolt viscosity given is that calculated from measurement of the kinematic viscosity.

In Table I below, several comparable runs are shown for conversions of decenev-l.

Tsar.: I

Thermal conversion of decene-I R No Temp., Time, Pressure Pggilt Viscosity v I Pour Bromine Bpeciilc Neut Rcfr. n F. Hours Gauge Charge 210 F. Point No. Gravity No. Index 400 9 150 1. 78 37. 92 76. 4 20. 8 400 20 100 0.8 51.65 129.5 15 14.5 510 300 6. 43 40. 79 145 22. 6 500 50 5. 6 60. 95 128. 5 y --30 11. 3 505 100 12. 9 60. 01 130. 4 -30 8. 5 510 10% 300 48. 6 44. 92 143 -20 17. 0 600 10 600 43. 2 43. 67 149 -15 18. 0 603 l5 210 57. 5 44. 81 147 -25 505 20 200 66. 3 45. 16 143 10 15. l 650 3 250 34. 0 45. 51 142 -10 16. 2 655 5 100 52. 9 43. 66 140. 5 -5 21. (l 650 10 250 64. 3 45. 13 142 5 17. 0 652 15 350 65. 3 44. 46 142 -5 17. 5 650 1954 250 66. 5 45. 32 141 -10 15. 6 660 954g 500 31.4 44. 88 135 -l0 14. 5 700 954 800 40. 0 42. 54 130. 9 -10 13. 7 700 1 300 33. 8 47. 69 136. 5 -20 l5. 0 700 3 200 4B. 4 50. 20 131. 7 -30 15.0 705 5 100 38. 8 48. 82 128. 2 -30 12. 2 703 9 850 18. 2 43. 21 95. 0 750 (l) 300 36. 6 44. 34 133. 7 15 19. 5 N' 750 3 600 30. 0 40.31 116. 3 10 23. l l. 750 5 650 26. 0 40. 31 109 -30 21. 5 0. 745 9 1, 100 9. 6 72, 57 27. 2 -5 27. 5 0. 800 (2) 500 26. 2 44. 66 134. 5 20 22. 9 N' 800 (3) 350 25. 7 43. 27 142 15 20. 2 0. 800 (4) 25. 6 43. 73 130 -20 21. 8 0. S50 5g 850 13. 5 41. 73 112. 5 +10 29. 0 0. 850 6 2, 500 6. 3 119. 2 0 +45 45. 2 0.

(All reactions conducted in an atmosphere o! N g unless otherwise specined.)

" Run in atmosphere of air. Explanation of the following:

(l) Bomb discharged immediately alter one hour reaction time.

(2) Bomb discharged immediately after reaching 800 F., 13 minutes required for draining.

(3) Bomb discharged immediately alter reaching 800 F., 8 minutes required for draining;

(4) Bomb discharged immediately after 30 minute reaction at 800 F., 8 minutes required for draining. (5) Bomb discharged immediately alter reaching 850 F., 18 minutes required lor draining.

(6) Bomb discharged immediately after 30 minute reaction at 850 F., 3l minutes required for draining.

the bombs and their contents to the desired temperatux'e, and do not include the time intervals necessary to cool the bombs after heat to the bombs has been discontinued. In general, about one and one-half hours are required to raise the temperature from 60- 80 F. to '700 F., and about eight hours to cool thereafter to 60-80 F., in runs such as shown in the tables. However, as indicated above, substantially no polymerization occurs below 500 F. and little occurs between 500 F. and 600 F.; therefore, these times are of little signicance.

The examples given in the tables were made under directly comparable conditions. The products discharged from the bombs were vacuum topped to remove any unreacted charge and any low-boiling materials, leaving the synthetic oils of this invention as -a residue. To distinguish the synthetic oils from the distillate fractions, the reiined oils are therefore identified as residual oils. The latter term indentifles theoils from which unreacted materials and products of intermediate boiling range have been separated.

VIn the tables, the pressure is given in pounds per square inch, gauge pressure. The yield is given as weight per cent of the charge, although in each run there Was some material lost in the process so that the actual eillciency of the process was somewhat higher than indicated.

All of the tests and analyses to which the residual oils in the tables were subjected are well known standard tests. In this connection, it

Referring more particularly to Table I, it will be apparent that, although synthetic oils can be produced over a somewhat wider range of temperatures, the most desirable combination of high yield, high viscosity index, and low pour point occurs in the range of temperatures varying from about 600 F. to about 700 F., with times varying from about ten hours to about three hours respectively, and with a pressure of at least about 200 pounds per square inch. It will also be apparent that pressure above about 200 pounds per square inch is not a critical factor; however. as far as is known at present, pressures of around 500 to 1000 pounds per square inch appear preferable.

As shown by runs Nos. 25 through 29 carried out at temperatures of 800-850 F., yields of synthetic oils are generally not more than about 25 per cent. These yields are in contrast to yields of 35-65 per cent obtained at preferred operating conditions of 60o-750 F. for 20 hours to one hour. Furthermore, at the higher temperatures of 800-850 F., a substantial portion of the decene-I charge is degraded by cracking and other side reactions, such that recovered material is unsuitable for recycling. In a continuous oper-v ation at 800-850 F., therefore, the ultimate yield of synthetic oil is appreciably lower than the ultimate yield obtained in a continuous operation at the aforesaid preferred conditions at 600- 750 F.

This relationship is illustrated graphically by data presented in Figures 1 and 2. In Figure 1,

the speciilc gravity o! the recovered distillate is plotted against reaction time at various operating temperatures. As shown, the specic gravity changes only slightly when operating temperatures of 600-700" F. and times of hours to one hour are used. This is in contrast with the very great change in specic gravity at temperatures of 800-850" F. using even shorter reaction times to minimize degradation. Figure 2 shows the relationship between bromine number (or unsaturation) of the recovered distillate and reaction time at various operating temperatures. The change of bromine number at temperatures of 60o-750 F. with times of 20 hours to one hour, is much less than at the higher temperatures of 800-850 F.

A further illustration-of the value of a continuous operation under the conditions contemplated herein, is shown by the following example. was heated in an autoclave, equipped with stirring means, at 600 F.'for 10. hours. 'I'he maximum pressure developed during the reaction. or conversion period was 5000 pounds per square inch, and the autoclave was vented several times to reduce the pressure to 4000 pounds per square inch. The autoclave was cooled and then discharged. The material obtained was treated in the manner described above in connection with Table I. A second run was made in the autoclave under the same conditions, using 21.43 pounds of n-decene-l. The residual oils of the two runs were combined, and the combined oils constitute a yield of 38.4 per cent, by weight.

A quantity, 22.39 pounds, of n-decene-l Figure 3 is a graphic representation ot the effect of temperature and reaction time upon viscosity index; and

Figure 4 is a graphic representation of the effect of temperature and reaction time upon yield.

Figure 5 is a graphic representation of the effect of temperature and reaction time upon speciflc gravity.

Data for Figures 1 through 5 were obtained by a. series of tests made on decene-l. The yield at 700 F. and using a three hour reaction time was 48.4% weight percent of the charge, and the product had a viscosity index of 131.7 and a pour point of 30 F. It will also be noted that yields 2f about 65 weight per cent were obtained at The tests set forth in Table Il, below, were performed for the purpose of determining the type of olefins utilizable in accordance with the present invention, and serve to demonstrate the critical nature of the normal, alpha mono-olen reactants contemplated herein. Isobutylene, pentene-2, 2-ethyl hexane-1, and Ca-polymer are examples of materials which are either branched chain, or which contain their double bond in other than the alpha position. The octene-2 used comprised approximately 58 per cent of noctene-2 and approximately 42 per cent of noctene-l and serves a two-fold purpose, namely: to illustrate an olen having the double bond in the beta position (n-octene-2), and to demonstrate the necessity for a charge stock containing only a relatively small quantity of olens other than a normal alpha mono-olefin (as noctene-l) TABLE n Thermal conversion of other olejlns Temp., Time, Pressure Viscosity Pour Bromine Speciilc Neut. Olean F. Hours Gauge Yleld 210 F. v' I Point No Gravity No.

Propylene 610 10 1, 500 5. 9 30 30 62. 8 0. 7887 l. 4 D0 650 10 2, 400 8. 5 43. 6 -85 -25 46. 9 0. 9705 1. 3

650 9 1, 600 3. 0 37. 98 35. 8 30 28. 9 0. 8462 10 650 10 2, 325 2. 8 43. 79 0 44. 7 0. 8822 605 10 1, "-5 2. 5 30 -30 85. 8 O. 7778 1. 2 610 9% 900 9. 9 37. 67 85. 0 65 20. 5 0. 8204 0. l 650 9 1, 150 1. 5 34.04 51.7 -30 51.7 1.05 Octene'2 650 20 900 10. 5 37. 09 34. 8 -30 52. l 0. 8007 l 0 CPolymer 640 9 l. 74 Octelle-l 4. 600 28 1, 400 45. 0 43. 92 128. 4 -70 14. 3 0. 8338 0 l Do 610 l0 700 29. 0 43. 14 120. 2 70 14. 9 0. 8413 0 2 Dodeoene-l. 600 10 250 50. 0 45. 18 152. 6 +25 16. 2 0. 8294 0 2 D0 710 5 250 61. 4 43. 34 150 +45 15. 7 0. 8348 (l 2 Hcxadecene-l 660 11 200 54. 8 50. 47 146 +75 12. 8 0. 8368 0 3 4 Approximately 90% n-octene-l.

The residual oil had a pour point of F., a V. I. of 133.1 and a specific gravity of 0.8408.

The distillates recovered in both runs were also combined, and constituted 55.5 per cent, by weight, of the total charge. The combined distillates had a specific gravity oi.' 0.7612 and a bromine addition number of 94.6. A quantity, 19.76 pounds, of the recovered distillates was then charged to the autoclave and heated at 600 F. for ten hours. In this run, the maximum pressure developed was 1900 pounds per square inch. The residual oil obtained in this run was 28.3 per cent, by weight, and recovered distillate represented 67.6 per cent, by weight, of the charge to the autoclave.

An indication oi' the interrelationships between temperature and reaction time upon the characteristics and yields of the synthetic oils may be obtained by reference to the appended drawings. in which:

From inspection of the results set forth in Table II, it is apparent that the yields from all olens other than normal, alpha'mono-olens of six to twelve carbon atoms, are very low and none of the products therefrom has a satisfactory combination of characteristics. It should be noted in connection with the n-octene-2 example, the yield and characterizing properies of the oil product would be of even lower calibre if the charge were substantially pure n-octene-2. A comparison of the run with the crude octene-2 with those involving octene-l shows a substantial difference in yield, 10.5 percent as compared with 29.6 to 45.0 per cent. Most striking, perhaps, is the great difference in V. I., 34.8 for the octene-2 product compared with 1262-1284 for the octene-l products. The critical nature of olen structure is further revealed by the results with 2-ethyl hexene- 1, in which case the yield was but 1.5 peicent and the V. I. only 51.7.

'The influence of chain length of the normal, alpha mono-oleiin is shown by the results with butene-l and with hexadecene-l. The yield is but 3.0 per cent and the V. I. but 35.8, when butene-l is used. An undesirably highpour point of +75 F. characterizes the hexadecene-l product.

With octene-l, decene-l and dodecene-l greatly improved yields are obtained but with dodecene-l the pour points are far too high for the products to be considered satisfactory for most purposes.

From the foregoing and as stated hereinbefore, it is believed that, by adjustment of the reaction conditions, usable products can be obtained from straight-chain l-oleiins or mixtures thereof, having not less than six nor more than twelve carbon atoms per molecule, and this is particularly true, if the olefins contain not less than eight nor more than eleven carbon atoms per molecule.

It will be understood from the foregoing 'that the process contemplated herein is of thermal character and does not involve the use of catalysts, such as Friedel-Crafts catalysts, shown in the prior art mentioned above. Accordingly, the process is properly identified as thermal and noncatalytic.

We claim:

1. The method for preparing a viscous oil from a normal, alpha mono-olefin having between six and about twelve carbon atoms per molecule, which comprises: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of said olefin at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively.

2. The method for preparing a viscous oil from a normal, alpha mono-olen having between six and about twelve carbon atoms per molecule, which comprises: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of said oleiin at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively, and at an elevated pressure of at least about 100 pounds per square inch.

3. The method for preparing a viscous oil from a normal, alpha mono-oleiin having between six and about twelve carbon atoms per molecule, which comprises: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of said oleiin at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively; and separating from the reaction product thus formed a viscous oil.

4. The method for preparing a viscous oil from a normal, alpha mono-oleiin having between six and about twelve carbon atoms per molecule, which comprises: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of said olefin at a temperature between about 600 F. and about 700 F. for a period of time from about iive to twenty hours at 600 F. to about three to ve hours at 7 00 F.

5. The method for preparing a viscous oil from a normal, alpha mono-olefin having between about eight and about eleven carbon atoms per molecule, which comprises: thermally and noncatalytically heating a hydrocarbon charge consisting essentially of said olefin at a temperature between about 600 F. and about 700 for a period of time from about ve to twenty hours at 600 F. to about three to ve hours at 700 F.

6. The method for preparing a viscous oil from n-decene-l, which comprises: thermally and noncatalytlcally heating a hydrocarbon charge consisting essentially of said n-decene-l at a temperature between about 600 F. and about 700 F. for a period of time from about ive to twenty hours at 600 F. to about three to ve hours at 700 F.

7. The method for preparing a viscous oil from a normal, alpha mono-'olefin having between six and about twelve carbon atoms per molecule, which comprises: thermally and non-catalytically heating a charge consisting essentially of hydrocarbons containing at least about per cent of said normal, alpha mono-olefin, at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively.

8. The method for preparing a viscous oil from a mixture of normal, alpha mono-olens having between six and about twelve carbon atoms per" molecule, which comprises: thermally and noncatalytically heating a hydrocarbon charge consisting essentially of said mixture of olens at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively.

9. The continuous method for preparing a viscous oil from a normal, alpha mono-olefinl having between six and about twelve carbon atoms per molecule, which comprises: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of said olen at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively; separating from the reaction product thus formed a viscous Oil and a fraction containing said normal, alpha mono-olefin in unconverted form; and recycling said fraction under the said conditions of temperature and time.

10. A viscous oil characterized by high viscosity index and low pour point, and obtained by: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of a normal, alpha mono-olefin having between six and about twelve carbon atoms per molecule, at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively, and separating from the reaction product thus formed said viscous oil.

l1. A viscous oil characterized by high viscosity index and low pour point, and obtained by: thermally and non-catalytically heating a hydrocarbon charge consisting essentialy of a normal, alpha mono-olefin having between six and about twelve carbon atoms per molecule, at a temperature between about 600 F. and about 700 F. for a period of time from about iive to twenty hours at 600 F. to about three to ve hours at 700 F., and at an elevated pressure of at least about Y pounds per square inch, and separating from the reaction product thus formed said viscous oil.

12. A viscous oil characterized by high viscosity index and low pour point, and obtained by: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of a normal, alpha mono-olefin having between about eight and about eleven carbon atoms per molecule, at a temperature between about 600 F. and about 700 F. for a period of time from about five to twenty hours at 600 F. to about three to five hours at 700 F., and separating from the reaction product thus formed said viscous oil.

13. A viscous oil characterized by high viscosity index and low pour point, and obtained by: ther- 11 mally and non-catalytically heating n-decene-l, at a temperature between about 600 F. and about 700 F. for a period of time from about ve to twenty hours at 600 F. to about vthree to ve hours at '700 F., and separating from the reaction mixture thus formed said viscous oil. y

14. A viscous oil characterized by high viscosity index and low pour point, and obtained by: thermally and non-catalytically heating a charge consisting essentially of hydrocarbons containing at least about 80 per cent of normal, alpha monoolen having between six and about twelve carbon atoms per molecule, at a temperature between about 600 F. and about '150 F. for a period of time from about twenty hours to about one hour, respectively.

15. A viscous oil characterized by high viscosity index and low pour point, and obtained by: thermally and non-catalytically heating a hydrocarbon charge consisting essentially of a mixture of normal, alpha mono-oleilns having between six and about twelve carbon atoms per molecule,

at a temperature between about 600 F. and about 750 F. for a period of time from about twenty hours to about one hour, respectively, and separating from the reaction product thus formed said viscous oil.

FRANCIS M. SEGER.

ALEXANDER N. SACHANEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Oil and Gas Journal, March 28, 1935, pages 81to 96. 

1. THE METHOD FOR PREPARING A VISCOUS OIL FROM A NORMAL, ALPHA MONO-OLEFIN HAVING BETWEEN SIX AND ABOUT TWELVE CARBON ATOMS PER MOLECULE, WHICH COMPRISES: THERMALLY AND NON-CATALYTICALLY HEATING A HYDROCARBON CHARGE CONSISTING ESSENTIALLY OF SAID OLEFIN AT A TEMPERATURE BETWEEN ABOUT 600*F. AND ABOUT 750*F. FOR A PERIOD OF TIME FROM ABOUT TWENTY HOURS TO ABOUT ONE HOUR, RESPECTIVELY. 